Control of pathogenic organisms with halogenated phenoxycyclopentenones



United States Patent CONTROL OF PATHOGENI'C ORGANISMS WITH HALOGENATED PHENOXYCYCLOPENTENONES Edward D. Weil, Lewiston, and Jerome Linder, Niagara Falls, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Original application Oct. 29, 1962, Ser. No. 233,873, now Patent No. 3,347,929. Divided and this application Dec. 2, 1966, Ser. No. 635,929

Int. Cl. A01n 9/24; C07c 49/76 US. Cl. 424331 3 Claims ABSTRACT OF THE DISCLOSURE Halogenated phenoxycyclopentenones such as those of the formula wherein Z is either bromine or chlorine, A is a dibromoor a dichloromethylene group or a carbonyl group, X is either halogen, nitro, alkyl, phenyl, alkoxy, or carboxy (or when combined with the phenyl ring illustrated, forms a naphthyl group), and n is from 0 to 5, are employed as pesticides, especially to destroy fungi on plants and bacteria.

This is a division of our application S.N. 233,873, filed Oct. 29, 1962, now US. Patent 3,347,929.

This invention relates to new and useful aromatic cycloaliphatic ketone-ethers, processes for the production thereof, and methods for the use thereof as intermediates and as pesticides, e.g., fungicides and bactericides.

The compounds of this invention have the general formula:

where Z is a halogen of atomic weight between 35 and 81, and where A is selected from the group consisting of -CZ and (C=O)- and where X is a substitiuent selected from the group consisting of halogen, nitro, alkyl, phenyl, alkoxy,and carboxy, and n is an integer from 0 to 5; X may in addition represent a benzo radical (-CH=CHCH=CH) fused to the phenyl ring to form the naphthyl radical.

Specific examples of compounds of this invention are:

0 o I H 3,443,016 Patented May 6, 1969 "ice 0 O H II @012 max, (CHa)aCH-O o12 mQ-o -01.

0 O I 01' on CI 01, A 01 001110 c1, 01 on 01 I on 016-0 o12 01 II II 0 on 01 N02-0 o1, Q-o o12 O H (:00 on O 0 ll II C 012 Cl;

} c0011 l Br0 o o o o 0 11 ll Gimp or 012 o 0 II II c 012 01 on 01 ooorr 01 Q 0 0 II I C l C12 C1 C12 C4Hn00 0 CaHr3O o o 0 II II or Ch c1 o12 o 0 H ll 01 or; on, 0 012 c1 01 i 01 o c12 o- 0 Cl 01 011mm):

0 0 II II mu Gil Cl: G 0

C1sHa1 ZLA.

where A and Z are as previously defined with a phenolic compound of the structure:

where X and n are as previously defined.

Preferred ketones from the standpoint of cost and availability are tetrachlorocyclopentene-3,5-dione and hexachloro-2-cyclopentenone, though any ketone corresponding to the formula above may be used. No particular preference is had for phenols and any corresponding to the generic formula above is suitable. The preferred halogen which is substituted on the phenolic compound and on the ketone for reasons of economics and case of synthesis of starting materials is chlorine.

There is no criticality regarding the concentration of either the ketone or phenolic compound, but the reactants are preferably used in equimolar amounts or with the ketone in excess.

The reactants will react to some degree when admixed as aforesaid, but it is preferred to conduct the reaction in the presence of about one mole of an acid acceptor (base) per mole of phenolic compound. The acid acceptor (base) is believed to form the phenolate salt of the phenolic compound, said salt being the reactive moiety. We do not wish to be held to a theory of the mechanism of the reaction; the base employed may function either as an acceptor of the liberated HX or it may serve to form the phenoxide anion or both. Suitable bases are sodium or potassium hydroxide, carbonate, phenate, sodium metal, magnesium hydroxide, calcium hydroxide, lithium hydroxide, pyridine, quinoline, triethylamine, N-methyl morpholine, N, N-dimethyl aniline, N,N-diethyl aniline, or any other basic tertiary amine. Not much more than one mole of acid acceptor (base) should be used however, because excess amounts may react With the product. Where X is carboxy, an extra mole of base is used for each X group.

The reaction can be conducted from temperatures from about ambient up to about 200 degrees centigrade. At lower temperatures, the rate is too low to be practicable; and at higher temperatures, tars and by-product materials are formed. The reaction is operable at subor superatmospheric pressures, but is preferably run at or near atmospheric pressure.

The use of a solvent is not necessary, but solvents may conveniently be employed. Excess ketone or phenolic compound may be used as a solvent. Other convenient solvents include aliphatic or aromatic hydrocarbons, chlorocarbons, ethers, alcohols, ketones, or esters.

No catalyst is necessary for the practice of this invention, although with some of the more slowly reacting phenols, such as certain nitro phenols, a catalytic amount of copper or copper salt may be found to have an accelerating etTect on the rate of the reaction.

Reaction times ranging from several minutes to several hours are conveniently employed. Generally, the reaction can be terminated when titration of an aliquot shows that substantially one mole of equivalent halide has been liberated.

The compounds of this invention may be isolated by distillation or crystallization from the reaction mixture. In most cases, the salt formed by reaction of the liberated HX with the base employed may be removed by filtration or by washin the reaction mixture with water.

The products of this invention are useful as pesticides and as chemical intermediates. As pesticides, they may be used for the control of fungi and bacteria as is hereinafter shown. As intermediates, the compounds of this invention undergo ring opening reactions with bases to form new herbicidal carboxylic acids, as follows:

(M=Metal cation or alkyl) -0 -Zz Z Xn The preparation of the various embodiments of the invention are described hereinafter.

Example 1.Preparation of 3-(2,4-dichlorophenoxy)-2, 4,4,5,5-pentachloro-2-cyclopentenone A mixture containing 10 parts of sodium hydroxide in 20 parts of water is added to 82 parts of 2,4-dichloro- 000M phenol at 40 C. This solution is then added to a mixture XE l Xn ZC COOM containing 82 parts of 2,4-dichlorophenol and 145 parts 01122 and/or 0 of hexachloro-Z-cyclopentene-l-one. The entire mixture is heated on a steam bath. After 3 hours, 11.7 parts of H chloride were found out of a theoretical amount of 14.6

parts. The mixture was distilled to a pot temperature of 160 degrees centigrade at 0.1 mm. The undistilled material and/or was dissolved in hexane, filtered to remove any salts and X crystallized from hexane giving a parts of a crystalline 000M solid which melted at 70.5 to 73 degrees centigrade.

-o Analysis-Called. for C H Cl O 01, 59.8. Found:

I CHZ 59:8. Z 2 20 In a similar manner, the following 3-aryloxy-2,4,4,5,5- pentachloro-2-cyclopentenones were made from hexa- 0 chloro-Z-cyclopentenone.

Ex. Aryl Group Phenol Used Base Used M.P., 0. Theory Found 2 05H; CaHnOH NaOH 66.5-67.5 51.2 51.2

a @011 E aN(Etethy1) on 49.3 48.0

CH3 CH3 4 G @011 EtaN on 49.3 48.8

CH: CH:

5 cm- 0H=0H EtaN 91-925 49.3 48.9

c1- CIOH EtaN 91.54)? 55.8 55.8

01 01 7 01G 01011 EtaN 109-10 63.1 62.6

a to.meormon N-methyl morpholine 106-108. 5 44.0 43. 5

4 0 Example 10.Reaction of 3-(2,4,5-trichlorophenoxy)-2, II 4,4,5,5-pentachloro-2-cyclopentenone with a base to prepare corresponding ring-opening product.

X I RIR2NH 0 II Cl: C! X l 01 NaOH 01 C112: C 012:0 01-3-0010 0 0H and/or 1 2 comm: 01 i GHZ Compound 7 22.5 parts of compound 7+4000 parts of water and cc. of ten percent sodium hydroxide is heated to 60 de- 0 75 grees centigrade. The sodium hydroxide insoluble is filtered off and the resulting clear solution is acidified with concentrated hydrochloric acid. A solid forms which melts at 149 to 150 degrees centigrade after crystallization from a hexane-benzene solution.

Analysis.Calcd. for C H Cl O Neutralization equivalent; 431.5. Found: Neutralization equivalent by titration with 0.1-N NaOH to phenolphthalein end point, 432.

Example ll.Preparation of 1-(2,4-dichlorophenoxy)-2, 4,4-trichlorocyclopentene-3,S-dione A mixture containing 117 parts of tetrachlro-4-cyclopentene-1,3-dione and 326 parts of 2,4-dichlorophenol is added to a solution containing 51 parts of N-methylmorpholine in 326 parts of 2,4-dichlorophenol. This mixture is heated for 36 hours at 100 to 110 degrees centigrade. The excess dichlorophenol is distilled off and the resulting material is dissolved in benzene and filtered to remove any salts which formed. The benzene solution is partially evaporated. A crystalline solid came out which on further crystallization from benzene melted at 150 to 150.5 degrees centigrade.

Analysis.Calcd. for C H Cl O: Cl, 43.6. Found: 43.3.

Example 12.-Preparation of 1-phenoxy-2,4,4-trichlorocyclopentene-3,5-dione A mixture containing 117 parts of tetrachloro-4-cyclopentene-3-dione and 250 cc. of phenol is added to a solution containing 51 parts of N-methylmorpholine in 250 cc. phenol. This mixture is heated for 48 hours on a steam bath. The excess phenol is distilled off then the remaining material is dissolved in 250 parts of benzene and the salts are filtered off. The benzene solution is evaporated and the remaining contents distilled. The boiling point of the material is 129 to 132 degrees centigrade at 0.25 mm. The distilled material solidified. Melting point after crystallization from hexane, 57-9 degrees centigrade.

Analysis.-Calcd. for C H Cl O Cl, 36.6. Found: 35.9.

The compounds of the invention have utility as pesticides as well as chemical intermediates. In general, the compounds of the invention exhibit fungicidal properties and bactericidal properties, as shown below:

Example 13 3 (B-naphthoxy) -2,4,4,5 ,5 -pentachloro-2-cyclopentenone.

3 p-tert-butylphenoxy) -2,4,4,5 ,5 -pentachloro-2-cyclopentenone.

3 (pentachlorophenoxy -2,4,4,5 ,5 -pentachloro-2-cyc1opentenone.

1-phenoxy-2,4,4-trichlorocyclopentene-3,5-dione.

Example 14 Nutrient agar treated with 1-phenoxy-2,4,4-trichlorocyclopentane-3,5-dione at 0.02 percent was inoculated with spores of Staphylococcus aure-us and Escherichia coli bacteria. No bacterial growth occurred although the agar without the chemical supported vigorous growth of both species.

Example 15 and compounds of the formula:

wherein Z is a halogen of atomic weight between 35 and 81, A is selected from the group consisting of CZ and C=0, X is selected from the group consisting of halogen, nitro, alkyl, phenyl, alkoxy and carboxy and n is from zero to five.

2. A method according to claim 1, wherein the pathogenic organisms are fungi and the locus thereof is a plant.

3. A method according to claim 1, wherein the pathogenic organisms are bacteria.

References Cited UNITED STATES PATENTS 12/1959 Baker 16730 1/1960 Gruenhager 167-30 ALBERT T. MEYERS, Primary Examiner.

D. M. STEPHENS, Assistant Examiner.

US. Cl. X.R. 260590 

